CN103999266B - active material for battery pack - Google Patents

active material for battery pack Download PDF

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Publication number
CN103999266B
CN103999266B CN201280050119.9A CN201280050119A CN103999266B CN 103999266 B CN103999266 B CN 103999266B CN 201280050119 A CN201280050119 A CN 201280050119A CN 103999266 B CN103999266 B CN 103999266B
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active material
carbon
electro
particle
chemical activity
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CN103999266A (en
Inventor
S.郑
D.布雷塞尔
M.温特
S.帕瑟里尼
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Volkswagen AG
Albemarle Germany GmbH
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Volkswagen AG
Rockwood Lithium GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

For the preparation method of the active material of battery pack, including：Electro-chemical activity particle is provided；Optionally crush the electro-chemical activity particle；Add Organic Compounds; optionally in suitable organic solvent; and mix; the mixture is heated to temperature more than the decomposition limit of the organic compound and below the decomposition temperature of electro-chemical activity particle, so obtained active material and corresponding application and purposes under a shielding gas.

Description

Active material for battery pack
This application claims the priority for enjoying DE 10 2,011 084 646.
The priority document is by reference to being generally introduced in the disclosure（= incorporated herein by reference in its entirety）.
The All Files quoted in the application is all by reference to being generally introduced in the disclosure（= incorporated herein by reference in their entirety）.
The present invention relates to the active material for battery pack.
The prior art：
The application of battery pack, such as in the memory technology of electric vehicle or renewable energy (such as wind energy, solar energy etc.) Battery pack application, it is necessary to with it is available so far and/or it is commercially available compared with those it is significantly higher Rechargeable battery group than energy develops new technology.
Lithium-sulfur cell group is very promising technology for these application fields.This is because the reason of elemental sulfur (S8) By gravimetric capacitance（gravimetrische Kapazität）For 1672 mAh g-1, or in other words, its theoretical energy density is most Big 2600 Wh kg-1(energy density of the lithium-ion technology i.e. than being widely used is most 5 times high).
In addition, the use of sulphur and the electrode material based on sulphur provides further general advantage, it is such as especially natural solid " overcharge protection mechanism " that has, without healthy worry, Environmental compatibility, abundant raw material reserves and low exploitation- And production cost.
However, also there is a series of challenge being listed below using sulphur as cathode material：
- sulphur and compound (such as the Li based on sulphur2S) there is extremely small electricity and ionic conductivity.
- more lithium sulfide (Li that centre is formed in charge and discharge process2Sn, wherein 2< n <8) it is very easy to be dissolved in In organic electrolyte used.This causes non-conductive insoluble Li2S2And Li2S is deposited on cathode surface, thus in electrochemistry It is upper no longer available；On the other hand, these polysulfides can also be diffused into anode-side, and be used as Li2S2And Li2S is deposited on that In, this can cause the passivation of anode surface, or it is reduced and diffuses back into cathode side again there.Latter event claims Make so-called " shuttle ", it causes the increase of reduction and the self discharge of the specific capacitance of battery pack.
- but on the other hand, due to the excessively poor ionic conductivity of the active material addressed, in active material and Contact area as big as possible is needed between electrolyte.
- during repeating charge and discharge cycles by the volumetric expansion of repetition related to this and-reduction causes to cause electricity The change of pole form, and sulfur granules agglomeration is thus ultimately resulted in, the conductibility of very small electricity and ion has played negative work again With.In this case, the surface of only described particle-agglomerate becomes electro-chemical activity, since particle-agglomeration necessarily causes The reduction on the surface.This causes reduction (Jeon etc., Journal of Materials of obtainable specific capacitance again Processing Technology 143-144 (2003) 93-97)。
In short, its reality for causing to be significantly lower than theoretical possible capacitance and would generally quickly reduce in cyclic process can The capacitance reached.
Thus the poor efficiency for producing low cyclical stability and charge and discharge process is caused.
20 (2010) 9821-9826 and Ji of Ji ＆ Nazar Journal of Materials Chemistry etc. Nature Materials 8 (2009) 500-506 is provided to the good summary of the theme and introduction.
The discharge process of sulfur electrode generally can be described generally by following reactional equation very much：
16 Li + S8 --> 8 Li2S
Have been able to recognize according to the reactional equation, for using elemental sulfur as cathode material, lithium in addition Source is indispensable.Therefore mostly use lithium metal as anode, its during repeated charge-discharge cycles still under cover Form the risk of dendrite.
Partly, have attempted in the prior art, use the final product of discharge process, i.e. Li2S, is replaced as raw material For elemental sulfur.
Widely use Li2S is similar as the significant challenge of cathode material and the situation of elemental sulfur, because electrochemical reaction is worked as It is so identical.Initial product reactant has been used as only.
Corresponding prior art Electrochimica Acta 55 (2010) 7010- such as being known in Wang 7015；The Carbon such as Wang 46 (2008) 229-235；The Electrochemistry such as Wang Communications 4 (2002) 499-502；Hassoun & Scrosati Angewandte Chemie 49 (2010) 2371-2374；Wang Deng Adv. Funct. Mater 13, No. 6 (2003) 487-492；The Journal of Alloys such as Choi and Compounds 449 (2008) 313-316；54 (2009) 3708-3713 of the Electrochimica such as Zhang Acta； The Nature such as the Materials Science Forum 510-511 such as Choi (2006) 1082-1085 and Ji In Materials 8 (2009) 500-506.
The method referred in the prior art is usually limited to use elemental sulfur (S8) it is used as raw material.For example, describe by Technology (Y.-J. Choi etc., Journal of the Power Sources 184 of the sulfur granules carbon coating of sputtering-technology (2008), 548-552).However, this technology is extremely complex, therefore it is expensive, and therefore and due to the technology Limited blending capacity, it is not suitable for being amplified to commercial scale.
Further, it is described that sulphur heat is embedded in and/or is absorbed to and/or by various forms of mesoporous carbon compound Many different methods, wherein make use of the relatively low melting temperature (115 DEG C) of sulphur.However, it is equally also all very multiple Miscellaneous and usually require the carbon material using nanoscale and/or nanostructured, it is costly again.
Especially downstream is by the lithiumation of n-BuLi, such as Yang, Nano Lett. 2010,10,1486-1491 Described in, it is associated with the use of multiple other processing steps and a series of extra reagent, therefore be also it is expensive and It is not useable for commercial Application.
The use of polymeric nanofiber, such as Qiu, Electrochimica Acta 55 (2010), 4632-4636 Described in, due to the complexity of this method, only seldom it is hopeful to be converted into more extensive.Meanwhile consider whole system " battery Group ", weight obtained by reality is significantly reduced using larger amount of such a polymer (i.e. the additive of electrochemistry passivity) Measure capacity and weight and volume energy density.
In addition, also using elemental sulfur here, its relatively low melting temperature is also the weight in the embedded polymer substrate of sulphur heat The prerequisite wanted.
Very expensive multi-walled carbon nanotube (Yuan etc., Journal of Power Sources 189 (2009), 1141-1146) or nano wire be used to be formed the application of conductive carbon matrix and equally seem and use these with fairly large Material can less be carried out.
It should be particularly noted that sulphur is applied on carbon in many solutions recited above.This be only capable of again due to sulphur compared with Low melting point is realized.In addition, the arrangement especially consideration and the relevant volumetric expansion of lithiumation (~+22%, referring to He etc., Journal of Power Sources 190 (2009) 154-156)。
However, herein always it must be taken into account that due to these volume changes, as already mentioned, in charge and discharge process Change electrode shape.Therefore, sulphur is applied to the risk directly contacted that sulfur granules are always concealed on carbon, and is therefore hidden The risk for the particle agglomeration having been mentioned, and active material come off from carbon material and therefore lose the risk of electric conductivity, it is special It is not to realize volume energy density as high as possible if to be closely spaced as far as possible by particle and therefore make the particle Arrange as snugly as possible each other.
In addition, although on the one hand wish there is contact area as big as possible to ensure lithium ion and sulphur between sulphur and electrolyte Between as big as possible contact area, but cause the diffusion of solvable polysulfide ions on the other hand, this is subsequently resulted in The unfavorable satellite phenomenon of description, this is one of main difficulty in sulfenyl electrode material is developed.
It is known by simply mixed by 196 (2011) 343-348 of the Journal of Power such as Hassoun Sources Close obtained Li2S-C compounds.Li is not implemented2The uniform and/or homogeneous cladding of S particles.
It is aqueous by coating known to 174 (2007) 683-688 of the Journal of Power such as Moskon Sources Citric acid and the carbon-coated TiO of use that is then thermally treated resulting in2Particle.
Goal of the invention：
So, it is an object of the invention to overcome the shortcomings that known in the art, particularly consider that the technique then may Commercial Application.
Therefore especially to find cheap, effective and reliable method and prepare the active material for being used for battery pack.
In addition, the purpose of the present invention is be accordingly provides for the favourable active material of battery pack, corresponding electrode and Battery pack is in itself.
Technical solution：
By the method according to the invention, the mesh is realized with material according to the invention in accordance with the purpose of the invention 's.
Term defines：
Within the scope of the present invention, unless otherwise noted, the data of all amounts are interpreted as weight data.
Unless otherwise noted, in nanometer range or micrometer range dimension data by scanning electron microscopy (SEM) measure, or should so measure.
Within the scope of the present invention, term " room temperature " represents 20 DEG C of temperature.Unless otherwise noted, temperature data is with Celsius Degree (DEG C) provides.
Unless otherwise noted, the reaction and/or processing step be normal pressure/atmospheric pressure (i.e. 1013 millibars) into Capable.
Within the scope of the present invention, stating "and/or" not only includes every kind of arbitrary combination, but also it is respective to be also included within this All combinations of the key element referred in enumerating.
Detailed description of the invention：
Invention especially provides the preparation method of the active material for battery pack, this method comprise the following steps a)- D) or by these steps form：
A) electro-chemical activity particle is provided；
B) optionally the electro-chemical activity particle is crushed to using average of scanning electron microscopy measure less than 2 μm Particle size；
C) Organic Compounds are added, optionally in suitable organic solvent, and are mixed；
D) mixture is heated to more than the decomposition limit of the organic compound under a shielding gas, preferably above 300 DEG C of temperature, and the temperature below the decomposition temperature of electro-chemical activity particle, thus the Organic Compounds be decomposed into Carbon, and the carbon is deposited on as uniform layer on the surface of electro-chemical activity particle.
Within the scope of the present invention, the electro-chemical activity particle particularly Li used in the method2S particles.
Due to Li2The low-down ions of S and electrical conductivity, the average particle size particle size less than 2 μm of SEM measure is necessary , to obtain high specific surface area.
If used Li2S has had less than 2 μm of average particle size particle size, then grinding be it is unwanted (but still So it is possible).
Carbon compound to be added or carbon source must be so selected, less than the electrification when making it heat under a shielding gas Carbon is decomposed at a temperature of the melting temperature for learning active particle.
Be preferably used as carbon compound within the scope of the present invention is sugar, is particularly sucrose, or polyacrylonitrile.
Relative to sugar, polyacrylonitrile provides an advantage in that, i.e., it can be dissolved in n-methyl-2-pyrrolidone (NMP) in, this causes Li2Carbon coating on S particles evenly.The fact that can be obtained according to the efficiency improved in charge and discharge process Know.
However, outstanding result can be obtained when using sugar as carbon source.These are mostly significantly better than the known knot of document Fruit.
For the carbon compound decomposition into carbon, to be made to it in protective gas, preferably helium, neon, argon gas or nitrogen, especially It is preferred that under nitrogen at a temperature of 850 DEG C of highest, preferably 550 DEG C -750 DEG C heat 2-5 it is small when, preferably 3 it is small when.
Here, the heating to decomposition temperature can be carried out with any required rate of heat addition in principle, there is no shadow to product Ring, but due to putting into practice, preferably select the temperature slope with about 2-4 DEG C/min, especially 3 DEG C/min.
Heat or be kept at this temperature in the stove that can be known in the art, carried out preferably in tube furnace.
Then can be by the so obtained Li with carbon-coating cladding2S particles are further processed into electrode.Corresponding method is same Sample becomes subject of the present invention, and including step i)-iv) or be made of it：
I) provide according to above-mentioned active material prepared according to the methods of the invention；
Ii at least one conductive additive) is added, is optionally added to less a kind of suitable adhesive；
Iia other additive) is optionally added；
Iii these materials) are mixed；
Iv) dry obtained material.
Carbonaceous material is the example of available conductive additive.
Available carbonaceous material be preferably selected from carbon black, synthesis or natural graphite, graphene, carbon nano-particle, fowler Alkene or its mixture.
Available carbon black can for example obtain under title Ketjenblack (R).
It is preferred that available carbon black for example can be in trade name Super P(R)Or Super P(R)Obtained under Li.
The carbonaceous material can have at 1nm-500 μm, and preferably 5nm-1 μm, particularly preferred 10nm-60nm scopes are averaged Particle size.
Suitable adhesive is polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyoxyethylene (PEO), fiber Element, cellulose derivative, poly- (vinylidene fluoride-hexafluoropropene) copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE) (PTFE), benzene second Alkene-butadiene rubber (SBR) and Kynoar (PVDF).
Within the scope of the present invention, it is used as adhesive preferably using Kynoar (PVDF).
Other additive for example can be the lithium powder of coating.These can act as lithium storage agent to compensate actual work Property material lithium initial irreversible loss.However, it can usually abandon adding other additive.
Here, the active material can be with least one conductive additive and at least one suitable bonding Agent is mixed with conventional ratio.In the scheme of the present invention, active material:Additive:The weight ratio of adhesive is 4:5:1.
Then so obtained cathode material can be processed into electrode with this area usual manner.
For example, it can apply it on the aluminium foil as current-collector, nickel foil or Al/Ni- paper tinsels.
Still other conventionally known in the art current-collectors can also be used.
Such as extensive discussions in document, the selection of suitable electrolyte/liquid and suitable partition plate also has one Fixed effect is (referring to the J. Electrochem. such as Peled Soc., 136, No. 6 (1989) 1621-1625；Jin etc. Journal of Power Sources 117 (2003) 148-152；The Journal of Power such as Chang Sources 112 (2002) 452-460)。
Within the scope of the present invention, all electrolyte well known by persons skilled in the art can be used as electrolyte, including：Bag Organic electrolyte containing the conducting salt well known by persons skilled in the art containing lithium, and the ionic liquid comprising conducting salt, such as Double (trifyl) imines (PYR of 1- butyl -1- crassitudes14TFSI double (fluorosulfonyl) imine lithiums in) （LiFSI）Or double (trifyl) imine lithiums (LiTFSI)；Polymer dielectric/liquid comprising conducting salt, such as comprising LiTFSI (and optional PYR14TFSI polyoxyethylene (PEO))；With optional organic electrolyte, such as in TEGDME LiCF3SO3, in ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC)/propylene carbonate (PC) Any mixture in LiPF6And in the mixture of dimethoxy-ethane (DME) and 1,3- dioxolanes (DOL) LiTFSI or LiPF6Or LiBF4；Or ionic liquid, solid electrolyte and any combination.
Those following are selected from it is preferred that can be used：In double (trifyl) imines of 1- butyl -1- crassitudes In double (fluorosulfonyl) imine lithiums or double (trifyl) imine lithiums；Polyoxyethylene comprising LiTFSI；Comprising LiTFSI and PYR14The polyoxyethylene of TFSI；LiCF in TEGDME3SO3, in ethylene carbonate/dimethyl carbonate/carbon LiPF in any mixture of diethyl phthalate/propylene carbonate6, in dimethoxy-ethane/1,3- dioxolanes LiTFSI, the LiPF in dimethoxy-ethane/1,3- dioxolanes6, in dimethoxy-ethane/1,3- dioxolanes LiBF4, 3:LiCF in 7 tetraethyleneglycol dimethyl ether (TEGDME)/1,3- dioxolanes3SO3And its mixture.
What it is particularly preferably as electrolyte is 3:In 7 tetraethyleneglycol dimethyl ethers (TEGDME)/1,3- dioxolanes LiCF3SO3。
Within the scope of the present invention, the partition plate that can be used is to be selected from those following：Polypropylene and/or based on polyacrylic Partition plate, the partition plate based on glass fibre, ceramic separator and its mixture or composition.
They can also act as partition plate at the same time in the case of polymer-and solid-electrolyte.
What it is particularly preferably as partition plate is three layers-film partition plate, such as Celgard(R)2325 provide.
The importance of the present invention is as solvent, because otherwise will give birth to when preparing the active material without using water Into Li2O and H2S。
Thus, it will " losing " described active material.
Invention further provides active material prepared in accordance with the present invention to be used as lithium-metal-and/or lithium-ion electricity The purposes of cathode material in the group of pond.
The present invention has the advantages that some are notable, will hereinafter enumerate some of them：
Except being considered to have relatively low specific capacitance (1166 mAh g in theory-1), by lithium sulfide (Li2S) it is used as living Property material contains some advantages relative to elemental sulfur：
Because Li2S lithiumations, thus its except can be used in lithium-sulfur cell group and in addition to, additionally it is possible to lithium-ion- It is used as cathode material in battery pack.This makes it possible for other anode materials [such as graphite, silicon, the tin in addition to lithium metal Deng] and therefore material presented herein can be unrelated with using lithium metal in anode-side.
The advantages of this is one huge for actual availability, because as it was previously stated, containing to be formed using lithium metal The risk of dendrite.
Secondly, which raises the possible flexibility of use of the material, and allow and all business derived from lithium-ion technology Successful or following anode material is used together in industry.
In addition, use Li2S contemplates during the lithiumation of sulphur that the volume for causing carbon outer casing rupture is swollen as raw material It is swollen.In this way Li is surrounded during charge and discharge algorithm is repeated2The carbon-coating of S particles also keeps complete.
As a result, the specific capacitance (and therefore improving the energy density of battery) actually obtained can be improved, hence it is evident that improve Cyclical stability, reaches the efficiency of almost 100% charge and discharge cycles.
In short, this can realize considerably higher accessible period, particularly if only being provided in whole system Limited lithium ion deposit rather than during as using providing the lithium ion of a large amount of excess in the case of lithium metal.In view of making The material is used in by the use of such as graphite as the Li-ion batteries piles of anode, and this is especially most important as cathode material, because Exterior lithium source is provided to be exactly no in such system.
In addition, uniform carbon shell equally significantly improves the electric conductivity of made active material.This causes Li2S Grain and its agglomerate do not occur that their electrochemical deactivations will be caused and thus can no longer provide the electricity of further charge and discharge process Insulation.
However, the uniform carbon shell particularly effectively prevent dissolving polysulfide in the electrolytic solution migration and its It is deposited on cathode surface on (associated with the electrochemical deactivation for depositing active material here) and anode surface (with increase Anode passivation and especially into so-called " shuttle " phase being responsible for the battery system self discharge based on sulphur Association).
In addition, uniform carbon shell prevents sulphur-or Li2Therefore physical contact between S- particles simultaneously effectively prevents following Particle agglomeration during ring.
Within the scope of the present invention, preferably using Li2The raw material of S rather than elemental sulfur as cathode.
Within the scope of the present invention, one kind " microreactor " of following demand is met to the electro-chemical activity particle preparation：
The soluble polysulfide of-prevention, which is diffused into cathode surface and/or anode surface and deposits, (to be passivated and " wears there Shuttle mechanism ")；
- particle agglomeration is prevented in charge and discharge process；
- ensure electrical contact with current-collector.
Ensure that " shell " of the microreactor is permeable for electrolyte at the same time within the scope of the present invention, with true Protect lithium ion and be transmitted to active material.
In addition consider known due to volume change caused by lithiumation and de- lithium.
Carbon is used for " shell of reactor ", because the solvable polysulfide that carbon has high electric conductivity and long-chain is protected Stay in the inside of " reactor ", but permeable electrolyte/liquid and lithium ion at the same time.
By using Li2S replaces elemental sulfur as raw material in addition using advantages below：
- Li2S has the fusing point more considerably higher than elemental sulfur, and more specifically it is about 938 DEG C.
- these higher temperature for the method according to the invention for being used to prepare active material, i.e., for It is necessary to apply on grain for uniform carbon-coating or carbon shell.
- due to " it is expected that " volumetric expansion occurred therewith is also thus anticipated to lithiumation, it need not worry due to this Volumetric expansion and damage the carbon shell.
- because Li2S has contained lithium, so it is not absolutely necessary to use lithium metal in anode-side, but can also Consideration uses other anode materials.
The method of the present invention use cheap materials (such as sugar, acetonitrile and polyacrylonitrile) carry out, it means that huge warp The advantages of in Ji and at least part ecology.
The method of the present invention is method generally of low cost, therefore it need not build numerous and diverse equipment.Therefore can Rapidly and easily to realize very much commercial Application.
Do not need electrolyte/liquid of a small amount of decisive influence battery pack cost only in the method for the invention, and Only small amounts of use additionally astoundingly improves this battery pack in the specific capacitance of raising, the efficiency of higher and improvement Cyclical stability meaning on performance.
Moreover, the method for the present invention can be converted easily to commercial scale, without it is larger financially and its He expends.
The result realized when using active material prepared in accordance with the present invention is better than the most of results announced in document.
In this regard, for more preferable comparability, it shall be noted that the value of the specific capacitance of acquisition is always based on being used as active material Li2The ratio meter of S.
The embodiment of some schemes of active material according to the present invention can be characterized as below：
Scheme 1 is the active material for battery pack, wherein it includes the electro-chemical activity for coating/being coated with uniform shell Particle.
Scheme 2 is according to the active material of scheme 1, wherein the electro-chemical activity particle is Li2S particles.
Scheme 3 is according to the active material of scheme 1 or 2, wherein the shell has high electric conductivity.
Scheme 4 is according to the active material of one or more aforementioned schemes, wherein the shell is that electrolyte is permeable.
Scheme 5 is according to the active material of one or more aforementioned schemes, wherein the shell includes carbon.
Scheme 6 is according to the active material of one or more aforementioned schemes, wherein being contained in the carbon in the shell to have by oneself Machine carbon source.
Scheme 7 is according to the active material of one or more aforementioned schemes, wherein the carbon being contained in the shell is by having The thermal decomposition of machine carbon source is made.
Scheme 8 is according to the active material of one or more aforementioned schemes, wherein the carbon being contained in the shell passes through sugarcane The thermal decomposition of sugar or polyacrylonitrile, is preferably made up of the thermal decomposition of polyacrylonitrile.
Scheme 9 be according to the active material of one or more aforementioned schemes, wherein it is described coat/be coated with uniform shell Electro-chemical activity particle is added with conductive additive.
Present invention additionally comprises the active material prepared using active material according to the present invention or by the method for the present invention Manufactured battery pack, and active material or mutually applied by active material prepared by the method for the present invention according to the present invention On the way.
Various embodiments of the present invention, such as but be only not those of each dependent claims, herein can be with Any-mode is combined with each other.
The obtained carbon-coating on the surface of electro-chemical activity particle of special measure by the present invention is homogeneous, Even and closing layer.This by being by the material being carbonized and the method being known from the state of the art that active material mixes It is not getable.
The present invention is illustrated now with reference to following unrestricted drawings and examples.
Brief description of the drawings：
Fig. 1 shows three width charts of three electrodes of measurement, wherein using by the sucrose as carbon source, according to this hair The Li of bright method carbon coating2S is as active material.Preparation is carried out according to Examples 1 and 2.
The figure of specific capacitance (in terms of mAhg/ sulphur) and efficiency (in terms of %) to cycle count is wherein drawn in each case.
Chart 1 shows the measurement carried out with the mA of 100 μ l electrolyte and C/50=0.02755；Chart 2 is shown with 45 The measurement that the mA of μ l and C/50=0.02635 is carried out；Chart 3 shows the survey carried out with the mA of 30 μ l and C/50=0.02420 Amount.
Measured three times for all, frame conditions are identical in each case：
C- speed：C/50
The C- speed of C/50 is electrode under the complete Theory capacitance of inherence typically when 50 is small（Put-）/ charge and apply Current density.
Constant current is circulated in the voltage range of 1.2-3.5V
Electrode area：1.13 cm2
(use sucrose as carbon source and change electrolyte dosage based on the Li coated with carbon2The constant current of the electrode of S follows Ring：The chart on top：100 µl (C/50 ≙ 0.02755 mA)；The chart at middle part：45 µl (C/50 ≙ 0.02635 mA)；With the chart of lower part：30 µl (C/50 ≙ 0.02420 mA).The C- speed of application: C/50.Blanking voltage：1.2 and 3.5 V vs. Li+/Li)。
Fig. 2 shows three width charts of three electrodes of measurement, wherein using by the polyacrylonitrile as carbon source, according to The Li of the method carbon coating of the present invention2S is as active material.Preparation is carried out according to Examples 1 and 2.
Chart 1 shows the measurement carried out with the mA of 60 μ l electrolyte and C/50=0.01524；Chart 2 is shown with 45 μ The measurement that the mA of l and C/50=0.01617 is carried out；The survey carried out with the mA of 30 μ l and C/50=0.01422 is shown with chart 3 Amount.
It is identical with Fig. 1 for all measurements, frame conditions.
(use PAN as carbon source and change electrolyte dosage based on the Li coated with carbon2The constant current of the electrode of S follows Ring：The chart on top：60 µl (C/50 ≙ 0.01524 mA)；The chart at middle part：45 µl (C/50 ≙ 0.01617 mA)； The chart of lower part：30 µl (C/50 ≙ 0.01422 mA).The C- speed of application: C/50.Blanking voltage：1.2 and 3.5 V vs. Li+/Li)。
Fig. 3 shows the chart for measuring electrode according to prior art, and wherein sulphur has 30 μ l electrolysis as active material The mA of liquid and C/50=0.01358.
Frame conditions are identical with Fig. 1 and 2.
(the constant current circulation of the electrode based on sulphur.The C- speed of application: C/50 ≙ 0.01358 mA.Blanking voltage： 1.2 and 3.5 V vs. Li+/Li)。
Fig. 4 shows two width X-ray diffraction charts.Upper chart shows raw material Li2The X-ray diffraction chart of S.Lower chart Show with the method according to the invention in 550 DEG C of Li coated with carbon2The X-ray diffraction chart of S.
Thus it is apparent from still maintaining Li after carbon coating2The structure of S.
Embodiment 1- prepares active material：
By 3g Li2S is by ball milling (the 30g ZrO of the 10ml acetonitriles as lubricating auxiliary agent2Ball) grinding, to reduce average Particle size.
Here, the grinding is carried out 20 minutes with 200-400 revs/min, then stop 10 minutes.The process repeats 30 It is secondary.
Then, by Li ground 9g2S and 1g sucrose, and by Li that 9g is ground in second lot2S and 1g polypropylene Nitrile solution (being made of 1g PAN and 9g NMP) mixes 30 minutes in each case in mortar.
Then mixture is transferred in tube furnace.
There, temperature is increased to 550 DEG C from room temperature with 3 DEG C/min of the rate of heat addition in a nitrogen atmosphere, in nitrogen By the temperature under atmosphere（Isothermal）Keep 3 it is small when.
Embodiment 2- prepares active material：
The method in embodiment 1 is repeated first.
It is a difference in that in tube furnace, is in a nitrogen atmosphere raised temperature from room temperature with 3 DEG C/min of the rate of heat addition To 300 DEG C, and by the temperature keep 2 it is small when.
The temperature is then increased to 750 DEG C and in a nitrogen atmosphere with the identical rate of heat addition（Isothermal）Keep 3 it is small when.
Embodiment 3- prepares electrode：
By the active material prepared in the embodiment 1 of each 40g and 50g Super P(R)Li is in mixer (ball mill) With 200-400 revs/min mixing 1 it is small when, then suspend 10 minutes.By the process in triplicate.
Then in each case by the PVDF solution of 100g 10% with 300-600 revs/min mixing 1 it is small when, then temporarily Stop 10 minutes.The process is repeated twice.
When by obtained product, drying at room temperature 24 is small in the drying chamber, then further when 60 DEG C of dryings 2 are small, at 80 DEG C When drying 2 is small, and when 100 DEG C of dryings 2 are small.
With through dry cathode material electrode is prepared by the way that the component is arranged in " bag ".Al/Ni current collections are used herein Device, 0.5 M LiCF3SO33:Electrolyte and Celgard are used as in the TEGDME/1,3- dioxanes of 7 ratios(R)2325 conducts Partition plate.
Embodiment 3- prepares electrode (comparative example) according to the prior art
Embodiment 2 is repeated, is simply used as active material using sulphur.
As a result：
Measured with the electrode according to made of embodiment 2 and embodiment 3 (comparative example), its result is plotted in Fig. 1, and (C- is applied The Li covered2S；Raw material：Sucrose) and the 2 (Li of C- coatings2S；Raw material：Polyacrylonitrile) and Fig. 3 (sulphur, uncoated=contrast Example) in.
, it is obvious that electrode is with than the active material with the present invention according to prior art from the chart of Fig. 1-3 The significantly lower efficiency of electrode.
In addition, it is obvious that the electrode of the active material with the present invention compared with electrode according to prior art with carrying High cyclical stability.

Claims (16)

1. the preparation method of the active material for battery pack, the described method comprises the following steps a)-d) or by these step structures Into：
A) electro-chemical activity particle is provided,
B) the electro-chemical activity particle is crushed to using average particle size particle size of the scanning electron microscopy measure less than 2 μm,
C) Organic Compounds are added, and are mixed,
D) mixture is heated to more than the decomposition limit of the organic compound and described under a shielding gas Temperature below the decomposition temperature of electro-chemical activity particle, thus the Organic Compounds are decomposed into carbon, and the carbon is as equal Even layer is deposited on the surface of the electro-chemical activity particle, it is characterised in that uses Li2S as electro-chemical activity particle, When the temperature of 550-750 DEG C of scope is wherein heated in step d), and keeping 2-5 small the temperature at said temperatures.
2. the method according to claim 1, wherein step c) carry out in suitable organic solvent.
3. according to the method for claim 1 or 2, wherein in step d) at said temperatures by the temperature keep 3 it is small when.
4. according to the method for claim 1 or 2, it is characterised in that reduce the particle of the electro-chemical activity particle by grinding Size.
5. method according to claim 4, it is characterised in that the grinding is ball milling and/or hand-ground.
6. according to the method for claim 1 or 2, it is characterised in that be used as organic carbon chemical combination using sucrose and/or polyacrylonitrile Thing.
7. according to the method for claim 1 or 2, it is characterised in that using polyacrylonitrile as Organic Compounds, and use N- N-methyl-2-2-pyrrolidone N is as solvent.
8. purposes of the active material prepared according to one of preceding claims in electrode and/or battery pack.
9. the active material prepared according to one of claim 1-7 is as the moon in lithium-metal-and/or lithium-ion-battery pack The purposes of pole material.
10. preparing the method for cathode material, the described method comprises the following steps：
I) active material prepared according to one of claim 1-7 is provided,
Ii at least one conductive additive) is added,
Iii the material) is mixed,
Iv) dry obtained material.
11. method according to claim 10, wherein in step ii) at least one suitable adhesive of addition.
12. according to the method for claim 10 or 11, wherein in step ii) and step iii) between there is step iia):
Iia other additive) is added.
13. according to the method for claim 10 or 11, it is characterised in that it is by step i)-iv) form.
14. method according to claim 12, it is characterised in that it is by step i)-iv) form.
15. according to the active material for battery pack prepared according to the method for one of claim 1-7.
16. for the active material of battery pack, it includes the electro-chemical activity Li for coating and/or being coated with uniform carbon shell2S- Particle, wherein the carbon being contained in the shell is made up of the thermal decomposition of sucrose or polyacrylonitrile.
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